Unsaturated ureido ethers and polymers thereof



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United States Patent UNSATURA'IED UREIDO ETHERS AND PDLYMERS THEREOF Sidney Melamed, Philadelphia, Pa., assignor to Rohrn & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application September 7, 1954, Serial No. 454,595

18 Claims. (Cl. 26ll77.5)

This invention relates to novel and improved ureidoalkyl vinyl ethers, polymers thereof and processes of making the ethers and their polymers.

The ethers of the present invention comprise ethylenically unsaturated polymerizable compounds falling within the following general formula wherein A is a cyclohexylene group or an alkylene group of 2 to 18 carbon atoms, of whicha chain of at least two is connected between the adjoining nitrogen and oxygen atoms, R is selected from hydrogen and a monovalent hydrocarbon group of 1 to 18 carbon atoms, R is an aliphatic or cycloaliphatic hydrocarbon group of 1 to 24 carbon atoms, and R2 is selected from H and aliphatic or cycloaliphatic groups of 1 to 24 carbon atoms. It is characteristic of the compounds of this invention that each N atom of the urea is attached to at least one essentially non-polar group and carries no reactive hydrogen atom or only one reactive hydrogen atom. The peculiar and distinctive character of the new ethers is apparently 2 such as ureidoethyl vinyl ether, can be made by reacting an aminoalkyl vinyl ether, such-as aminoethyl vinyl ether, with a water-soluble cyanate, such as potassium cyanate, in the presence of an acid, such as sulfuric acid, at a temperature of 0 to 50 C. and a pH of at least 6.8. These ethers are polymerizable under certain conditions. The

attributable to this structure as will be pointed out hereinafter.

Aminoalkyl vinyl ethers are known. They are not readily polymerized with small amounts of acid catalysts or free radical catalysts. Alkyl vinyl others, on the other hand, are readily polymerized with acid catalysts and are but slightly aifected by normal concentrations of peroxidic catalysts. In contrast the substituted ureidoalkyl vinyl ethers of this invention are polymerizable under the influence of azo catalysts, although they do not respond to catalytic quantities of acids or to peroxides whether organic or inorganic under the various conditions which are known to result in polymerization of many vinylidene compounds including other types of vinyl compounds.

Amino-substituted vinyl ethers have been reported to polymerize with molar proportions of sulfur dioxide to give products of relatively low molecular weight which contain units from sulfur dioxide. It has been found that ureidoalkyl vinyl ethers of the present invention likewise polymerize with molar proportions of sulfur dioxide to form products which have low molecular weight and which include sulfur dioxide as a component. These polymers dilfer in bQih these respects from the polymers of high molecular weight which are formed in the presence of azo catalysts from ureidoalkyl vinyl ethers. The ureido group actually destroys the ability of alkyl vinyl ethers to respond to catalytic amounts of polymerization initiators of acid type.

The polymers of this invention furthermore are dis tinct from polymers of allyl derivatives, such as allylurea, which forms only low molecular weight polymers at best. Allylurea, for example, is a powerful chain transfer agent which inhibits formation of other polymers.

Ureidoalkyl vinyl ethers of the formula ethers of the present invention cannot be made by this reaction but require special procedures as will be pointed out.

Attempts to obtain CH2 CH-O-C2H4NHCON (CH3 )2 and closely related compounds, such as by reacting CH2 :=CH" OC2 H4 NH2 I with dirnethyl carbamyl chloride -(("CH3)2NCOC1), fail completely since the unsaturated vinyl group is lost, apparently by cyclization.

Surprisingly, however, it has been found that numerous of the compounds of the invention within the scope of Formula I are of exceptional stability so that they can be isolated without similar loss of unsatura'tion by cyclization.

One such group .of stable compounds are those having the structure of the following formula CH2:CHO-ANRCONHR I 11 where A, R, and R are the same as defined hereinbefore. Preferred compounds are those in which R is an alkyl or cycloalkyl group and R is saturated.

Another group includes those having the formula in which R and R are defined, hereinabove, Y is an alkylene group of 1 to 7 carbon atoms, R is an alkyl group of l to 4 carbon atoms, and R is an alkyl grou of 1 to 4 carbon atoms. a

A fourth group comprises compounds of the general formula where R and R are as defined above and Z is a cyclohexylene group or an alkylene group of 4 to 18 carbon atoms of which a chain of at least 4 is connected between the adjoining nitrogen and oxygen atoms.

The compounds of Formula II are made by the reaction of isocyanates of the structure RNCO on amino alkyl vinyl ethers of the formula CH2:CHO-A-NHR VI R and R being as defined above. The reagents are used in about equimolar proportions or an excess of either may be used. The reaction is effected at a temperature of 10 C. to l00 C., preferably 10 C. to 35 C. Inert solvents, e. g. benzene or petroleum ether, may be used but are not necessary in all cases. .Typ'ical'vinyl e'tl'rei's (Formula VI) that may be used are:

CH2: CHOC (CH3) zCHzCH (CH3) NHz CH2 CHOCI-IzCHzCH CH3) (CH2) 3C CH3) zNHz CH2 CHOCH2C( CH3) 2CH2NH2 CH2: CH CHzCH CH3) NHCHs The vinyl aminoalkyl ether may have an N-substituent (R) other than hydrogen and the preferred methyl group, such as ethyl, butyl, phenyl, methylphenyl, butylphenyl, benzyl, methylbenzyl, cyclo hexyl, and so on, typical compounds then being CH2=CHOCH2CH2NHC6H5 (distilling at l28130 C./9 mm),

CH2=CHOCH2CH2NHC4H9 (distilling at 88-99 C./120 mm.),

CH2CHOCH(CH3 CHzNHCaHs (distilling at 7273 C./l20 mm.),

CHz=CHOCHzCH2NHCHzCeHs CH2 =CHOCH2CH (CH3) NHCsH4CH3 C2H=CHOCH2CH2NHC6H11 CH2=CHOCH2CH2NHCH2CH=CH2 CH2=CHOCH2CH2NHCH2CH=CHCH3 CH2=CHOCH2CH2NH(CH2) 9CH=CH2,

CH2=CHOCH2CH2NHC13H33 (2 double bonds soya amine), CH2=CHOCHZCH2NHC18H35 (oleyl amine),

CHg=OHOCHaCH2NHGHrU CH=CH CHFCHOGHCHINHI (from butadiene monoxide) CHFCHO HCHQNHI (from vinylcyclohexene monoxide),

CH2=CHOCH2CH2NHCHaCH2CECCHs, etc.

The last compound is available, for example, through the reaction of mcthylacetylene and ethylene oxide to yield CH3CECCH2CH2OH, which is converted to the chloride with thionyl chloride, the chloride being then reacted with ethanolamine to form the alcohol RNHCHzCHzOH CHz=CH0C6H1oNHz CH2=CHOCH2CH2C6H10C( CH3) 2NH2 (CeHm being the cyclohexyl nucleus in both cases).

CHz=CHOCH(CeH) CHzNHz GET-CHO crrzacnocrncnfcwna (CsHs)NH2 CH2=CHOCH2CHsOCHzCHzNHz CH2=CH0CH2CH2OCH2CH(CH3)NH2 CHz=CHOCHzCHzOCH2CH2NHCHs CH2=CHOCH2CH2OCH2CH2NHC6H5 CH2=CHOCHzCHzOCHZCH2NI-ICH2CGH5 CHz=CHOCHzCHzSCHzCH2NH2 CH2=CHOCH2CH2OCH2CH2NHC2H5 CH2:CHOCHzCI-IzOCHzCHzOCHzCHzNHz Typical isocyanates (RNCO) are: methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, isobutyl isocyanate, t-butyl isocyanate, amyl isocyanate, isoamyl isocyanate, cyclohexyl isocyanate, hexyl isocyanate, octyl isocyanate, decyl isocyanate, dodecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, oleyl isocyanate, tetracosyl isocyanate, fi-chloroethyl isocyanate, fl-nitroethyl isocyanate, 3-nitro- 3,3-dimethylpropyl isocyanate.

The compounds of Formulas III, IV, and V are made by the reaction of a disubstituted carbamyl chloride of the formula RR NCOCl VII in which R and R have the same definition as above with an amine of any of the following formulas respectively in which the symbols have the same definitions as above. The conditions of the reaction may vary widely. The temperature may be from 10 C. to C., preferably -10 to 50 C. Reaction is preferably effected in all cases in the presence of a basic acceptor for the hydrogen chloride liberated, such as excess of the amine reactant, or an inorganic base, such as NaOH, KOH, NazCOa, K2CO3, etc. The reaction may be eifected in an inert solvent such as benzene, toluene, xylene, petroleum ether or in a mixture of such a solvent with water.

Examples of the carbamyl chlorides of Formula VII that may be used are: dimethyl carbamyl chloride, diethyl carbamyl chloride, dipropyl carbamyl chloride, diisopropyl carbamyl chloride, dibutyl carbamyl chloride, di-isobutyl carbamyl chloride, diamyl carbamyl chloride, dihexyl carbamyl chloride, dicyclohexyl carbamyl chloride, dioctyl carbamyl chloride, didecyl carbamyl chloride, didodecyl carbamyl chloride, dihexadecyl carbamyl chloride, dioctadecyl carbamyl chloride, ditetracosyl carbamyl chloride, methyl ethyl carbamyl chloride, methyl propyl carbamyl chloride, methyl isopropyl carbamyl chloride, methyl butyl carbamyl chloride, methyl cyclohexyl carbamyl chloride, methyl octadecyl carbamyl chloride, ethyl isopropyl carbamyl chloride, ethyl octyl carbamyl chloride, ethyl hexadecyl carbamyl chloride, butyl octadecyl carbamyl chloride, hexyl octyl carbamyl chloride.

Representative amines of Formula VIII include all those listed above as representative of those of Formula VI in which substituent R is other than hydrogen.

Representative amines of Formula IX include as well as others listed under Formula VI.

produced involves the reaction of isocyanatoalkyl vinyl ethers of the structure Y, R and R being defined above, with primary or secondary amines of the formulas NHzR' and NHR'R respectively. The ethers of Formula XI are disclosed and claimed in copending application Serial No. 348,107, filed April 10, 1953, in the hands of a common assignee. Examples thereof include 2-isocyanatoisobutyl vinyl ether and ERNC CH2: CHOCI-i CH3 CH2C(CH3 zNCO Examples of the primary and secondary amines include methylamine, dimethylamine, ethylamine, diethylamine, methylethylamine, and so on within the scope of the definitions of R and R above.

In the new compounds of the present invention, the nitrogen atoms on each side of the urea residue or moiety are substituted by non-polar groups. This structure apparently accounts for the distinctive properties of the compounds as compared to compounds of the type CH2 CHOANRCONH2 as defined above. The properties are:

1. Reduced or no reactivity to such agents as aldehydes, e. g., formaldehyde.

2. Lower melting points and higher vapor pressures so that it is practical to isolate and purify the new compounds, especially those of lower molecular weights, by distillation.

3. Orientation at an oil-water interface such that the two hydrophobic groups extend into the oil layer.

4. Modified solvent power.

In addition, the new polymers have much greater chemical stability, especially against acids or heat as compared to the polymers of CH2:CHOA-NRCONH2; the new polymers are chemically stable in aqueous s o1u tions or dispersions under normal conditions of storage over long periods of time.

The structure of the monomeric compounds also markedly influences the properties of homopolymers and copolymers containing a major proportion of units derived from the new compounds. Such polymers have reduced or no reactivity, especially with such reagents as formaldehyde. Films, filaments, and other articles made of these polymers show surprisingly reduced sensitivity to water. While CH22CHOC2H4NHCONHCH3 (compound A) and CH2:CHOC2H4NHCONHC2H5 (compound B) are water-soluble, the homopolymers of the former (compound A) have only slight solubility in water and the homopolymers of the latter (compound B) are insoluble in water. In contrast, homopolymers of CH2 CHOCsHsNCHaCONHz are water-soluble. The simple methylol derivatives of the polymers of compounds A and B, however, obtained by reaction with formaldehyde are water-soluble, but can be insolubilized by prolonged baking or curing. In addition, the homopolymers of compounds A and B are substantially chemically stable in aqueous solutions or suspensions under normal conditions of storage over long periods of time. The new monomeric compounds are more compatible with other monoethylenically unsaturated compounds, such as the alkyl esters of acrylic and methacrylic acid in. which the alkyl group may be from 1 to 12 carbon atoms, vinyl acetate, vinylbutyrate, vinyl propionate, than monomers of the type CH2:CHOANRCONH2 so that copolymerization with the compounds can be more readily effected in a solution system. Furthermore, whereas emulsion copolymers can be. made containing a minor proportion of units derived from CH2 CHO--ANRCONH2 with other monoethylenically unsaturated comonomers, such as butyl acrylate, the polymer dispersions obtained are generally not mechanically stable so that impregnations or coatings made therewith must be made promptly after the preparation of the dispersion. In contrast, waterinsoluble copolymers of a minor proportion of units derived from the new compounds can be obtained by the emulsion polymerization system and the dispersions thus obtained are mechanically stable over long period of time, making it possible to store or ship the dispersions before making coatings, impregnations, or the like therefrom.

The new monomeric compounds are useful in many ways: as solvents, especially as components of insecticides; for modifying by reacting with cellulosic materials or other OH-group containing substances, such as polyvinyl alcohol, hydroxyethylcellulose, starch, in the forms of films, fibers, fabrics, etc. to modify water-retention properties or to modify the dyeing properties; as components of aminoplast resins such as urea-formaldehyde of melamine-formaldehyde resins; for making adhesives, cements, molding compositions, coating compositions, etc., tending to stabilize the preliminary condensates made on the alkaline side and to accelerate final cure on the acid side. In the final product, the ethers with relatively large hydrocarbon substituents provide an internal plasticizing action, while all of these ethers provide increased resistance to solvents and water for cured films or deposits of the resin made in this way.

Those of the new compounds in which the nitrogen atoms have a reactive hydrogen are useful as chemical intermediates to react with other compounds including aldehydes, such as formaldehyde, alkylene oxides, such as ethylene oxide, to form insecticides, fungicides, pharmaceuticals, textile assistants, resins, etc. V

The novel ureidoalkyl vinyl ethers can react with cellu lose, polyvinvyl alcohols, and other polyhydroxy compounds to give urea-modified materials which can be further reacted with formaldehyde. These ethers are thus useful in modifying cellulosic textile products and plastic materials. The vin oxyalkylureas having one or more large alkyl groups can thus impart hydrophobic properties to materials otherwise sensitive to water. The long chained materials can be used for permanent waterproofing of cellulosic fibers and the like. These compounds also react with nitrogenous fibers.

The new ureidoalkyl vinyl ethers containing hydrocarbon substituents of 8 to 18 carbon atoms have been found compatible with such vinyl resins as polyvinyl chloride. When added to these resins, as by milling, they impart a moderate degree of plasticization, but more particularly they stabilize the resin against degradation by actinic light. Similarly substituted ethers have been found effective as corrosion inhibitors when dissolved in oils. The lower members of the series exhibit insecticidal, miticidal, and ovicidal action.

The new monomeric ethers are polymerizable alone or in combination with each other and/ or with one or more other polymerizable unsaturated compounds. They are stable in absence of polymerization catalyst and do not 7 tend to cyclize. This is a distinctive property and surprising since such compounds as CH2 CH--OCH2CH2-NHCON (CH3) 2 cannot be isolated from the products obtained by the reaction of O (CHshNiiCl in accordance with the methods used herein; instead it appears that cyclization occurs producing a saturated compound which contains no polymerizable double bond.

The polymerization of the new compounds is effected in the presence of an acyclic azo compound. In such compound the -N=N group is attached to aliphatic carbon atoms, at least one of which is tertiary. Typical azo catalysts are azodiisobutyronitrile, azodiisobutyramide, dimethyl (or diethyl or dibutyl) azodiistobutyrate, azobis a,'y-dimethylvaleronitrile azobis a-methylbutyronitrile), azobis(a-methylvaleronitrile), dimethyl azobismethylvalerate, and the like. In these catalysts one of the carbons bonded to the tertiary carbon atom has its remaining valences satisfied by at least one element from the class consisting of oxygen and nitrogen.

To effect polymerization the ureidoalkyl vinyl ether and the acyclic azo catalyst are mixed directly or in the presence of an inert solvent and the mixture is maintained between 60 and 100 C. until the desired extent of polymerization is attained. For water-soluble ureidoalkyl vinyl ethers water may serve as solvent, if desired. Other solvents include methanol, ethanol, isopropanol, butanol, dimethylformamide, benzene, toluene, ethyl acetate, etc. The amount of catalyst may be varied from about 0.1% to about 5% of the weight of the ureidoalkyl vinyl ether. The polymerization is best carried out in an inert atmos phere such as nitrogen gas. a

For polymerization in solution concentrations of monomer from about to about 60% are generally desirable. The course of polymerization may be readily followed from the increase in viscosity of the solution. The catalyst may be added in increments, if desired, with or without additional solvent.

A 50% aqueous solution of a water-soluble ureidoalkyl vinyl ether has a viscosity of less than As on the Gardner- Holdt scale. After polymerization at 75 C. for 16 hours the viscosity is usually B to D, but may be carried to Z4. as conversion is carried further.

Polymerization in dimethylformamide results in a conversion of monomer to polymer at least as high as in water and usually higher for a given amount of catalyst, but the polymer formed is of lower molecular size than polymers formed in water. For example, a 50% solution of CHzzCHOCzI-LrNHCONHCl-Is in dirnethylformamide held at 75 C. for 16 hours readily develops a viscosity of G to I on the Gardner-Holdt scale, but conversion may be carried to a viscosity from D to Z4. The mixture is homogeneous at the end of the polymerization. For bulk polymerization the preferred temperatures are from about 70 to about 80 C. and the optimum proportion of catalyst is from 0.3% to 1% of the weight of the ureidoalkyl vinyl ether. Under a nitrogen atmosphere a satisfactory degree of polymerization is obtained in 10 to 20 hours.

The polymers which result are soluble substances unless diethylenically unsaturated comonomers are used. The homopolymers of CH2 CHO C2H4NHCONHCH3 CH2 CHOCsHsNl-ICONHCHs and CI-IztCHOCzI-IaNCI-IsCONHCHa are of limited solubility in water and are relatively insoluble in acetone and benzene. These polymers may be separated from their monomers by precipitation from their aqueous solutions, for example, by addition of a miscible solvent, such as acetone. These polymers, precipitated as with acetone, are white to light tan solids which can be dried under reduced pressure. A 50% solution, in a 1:1 volume ratio mixture of methanol and water, of the dried polymer has a viscosity of A to Z on the Gardner-Holdt scale. If these polymers are heated above 150 0., they lose their solubility.

With increase in the size of the alkylene groups comprising, A, Y, Z, R and R and of the groups R, R, R and R in ethers of the Formulas II, III, IV, and V, the polymers change from water-soluble to solvent-soluble. Thus with increase in size of such groups, the polymer becomes soluble in alcohols or benzene.

The ureidoalkyl vinyl ethers polymerize through their vinyl groups to form polymers having a multiplicity of ureido groups which are available for further reaction when the nitrogen atoms thereof carry reactive hydrogen atoms. It is probably through these groups that cerain of the polymers become cross-linked and insoluble when they are heated above 150 C. These reactive-hydrogen containing groups are also reactive to chemical reagents which combine with urea and like compounds, including aldehydes such as formaldehyde, ketones, isocyanates, isothiocyanates, and the like.

The polymers of the compounds of Formulas III and IV are distinguished from the others by their inertness to further chemical reaction, such as with formaldehyde, ethylene oxide, etc., by their stability and by their relatively completely non-polar character rendering them more soluble in organic solvents of both polar and nonpolar types.

The polymers of this invention are classed as high polymers since the polymers are built up of a large number of repeating units. Yet it must be pointed out that the degree of polymerization can readily be controlled by choice of solvent and other conditions of polymerization. In bulk polymerizations or in polymerizations in aqueous solutions polymers of 50,000 to 200,000 molecular weight may be obtained. In many organic solvents, such as dimethylformamide, alcohols, and ethyl acetate molecular weights can be obtained of the order of 10,000 to 20,000.

In contrast to alkyl vinyl ethers which copolymerize under the influence of organic peroxides but poorly and in some cases fail to enter into copolymers, the ureidoalkyl vinyl ethers of the invention have been found widely useful in copolymerizations. It has been found that these ethers can be copolymerized with other polymerizable olefinically unsaturated compounds, particularly vinylidene compounds, under the influence of a polymerization promoter of the free radical type, such as peroxides or azo catalysts, an acyclic azo compound being particularly useful and advantageous. With an azo cata lyst temperatures between 50 and about 100 C. are generally efiective for copolymerizing. Somewhat higher temperatures are useful when catalysts of the peroxidic type are used, temperatures between and 150 C.

being practical, the above temperatures being those observed for copolymerization in bulk or in solution. Temperatures between 0 and C. or more are useful when copolymerization is carried out in aqueous suspensions or in emulsions.

The same azo catalysts described above for use in forming polymers are used for preparing copolymers, particularly when the major portion of the monomers is a ureidoalkyl vinyl ether of the invention. The amount of catalyst may be varied between 0.1% and 5% of the weight of the monomers to be copolymerized. A range from 0.3% to 1% is preferred, at least at the start. Small amounts of catalyst may be added from time to time as copolymerization proceeds.

When a ureidoalkyl vinyl ether of the invention furnishes the minor portion of an interpolymer, however,

other free radical catalysts may prove desirable. For example, organic peroxides, such as butyl perhenzoate, or benzoyl peroxide, are suitable for polymerization in bulk or in solution, while ammonium persulfate and. the like are useful in the polymerization of dispersions.

As useful unsaturated compounds for forming the copolymers there may be used acrylic acid, methacrylic acid, esters of acrylic acid or methacrylic acid and monohydric alcohols such as methyl, ethyl, butyl, octyl, dodecyl, cyclohexyl, allyl, methallyl, undecenyl, cyanoethyl, dimethylaminoethyl, and the like; esters of itaconic acid and similar alcohols; esters from maleic, fumaric or citraconic acids, and likewise similar alcohols; vinyl esters of carboxylic acids such as acetic, propionic, butyric, and the like; vinyloxyalkyl esters such as vinyloxyethyl acetate, etc.; vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, octyl vinyl ether, allyl vinyl ether, hydroxyethyl vinyl ether, aminoethyl vinyl ether, aminopropyl vinyl ether, dimethylaminoethyl vinyl ether, vinyloxyethoxyethanol, vinyloxypropoxyethanol; methacrylonitrile or acrylonitrile; acrylamide, or methacrylamide, and N-substituted amides of these types; vinyl chloride, vinyl bromide, vinylidene chloride, l-chloro-l-fluoroethylene, or ethylene; l-acetoxy-l,3-butadiene; styrene, Z-Vinylpyridine, 4-vinylpyridine, or divinylbenzene; ethylene diacrylate or dimethacrylate, bis(vinoxyethyl)urea, vinoxyethyl acrylate, vinoxypropyl acrylate, etc. Where two polymerizable vinylidene groups occur in the same molecule, as in compounds toward the end of the above list, crosslinking results where more than one to two per cent thereof is used in forming the copolymer.

There are several important types of classes of interpolymers which should be particularly mentioned. Where it is desired to obtain new properties or variations in properties over the properties of the homopolymer of a ureidoalkyl vinyl ether there may be used about 1% to about 60% of one or more other polymerizable vinylidene compounds. Often 1% to 20% is the most useful range to promote the desired modification of properties. Some valuable examples of copolymers of this sort are those obtained with 1% to 20% of vinylpyridine and 99% to 80% of a unreidoalkyl vinyl ether of Formulas II and V and which have water-solubility in the salt form or are soluble in organic solvents, such as methanol, or in aqueous-organic solvent systems, such as aqueous methanol or aqueous acetone. These copolymers have marked affinity for cellulose. Again a copolymer from 1% to 20% of ammonium or alkali metal (i. e. sodium or potassium) salts of acrylic acid, itaconic acid, or methacrylic acid and 99% to 80% of a ureidoalkyl vinyl ether of Formula II is of interest because it'supplies properties peculiar to polymers of the ureidoalkyl vinyl ether and yet it can be cured or insolubilized by treatment with polyvalent metal ions, such as aluminum or calcium.

In another important category of iuterpolymers a ureidoalkyl vinyl ether of Formulas II and V is incorporated in minor amount with another polymerizable vinylidene compound to impart new properties thereto. Here 1% to 50% and preferably 1% to 20% of the ureidoalkyl vinyl ether is mixed with one or more other polymerizable vinylidene compounds and the interpolymer thereof is formed. The presence of reactive hydrogen containing ureido groups from the ether imparts a second stage reactivity to the interpolymers. The presence of such groups may impart such desired properties as solventresistance. craze-resistance, hydrophilic properties (from ethers with small alkyl groups), hydrophobic properties (from ethers with larger alkyl groups), thermal activity, reactivity toward such substances as aldehydes, and so on. The ureidoalkyl vinyl ethers may thus be used to modify copolymers for use in coatings, adhesives, films, fibers, castings, etc.

Copolymerization, as has been indicated, may be effected in bulk, in solution, or in dispersion. When the monomers to be 'copolymerized are water-soluble, they 10. r may be copolymeri'zed' in. aqueous solutions.v Solventsolublemonomers may behandled in inert organic solvents such as benzene, toluene, methanol, ethanol, bu,- tanol, acetone, methyl ethyl, ketone, dimethylformamide, ethyl acetate, ethylene dichloride, etc. Concentrations from about 10% to 60% are conveniently used. The course of copolymerization may be followed from the changes in viscosity or changes in; solubility. Monomers andcopolymer may be separated, if desired, by precipitau tion, extraction, distillation, or other conventional step.

Water-soluble ureidoalkyl vinyl ethers effectively.- solubilize considerable proportions of otherwise water-insoluble polymers of vinylidene compounds, such as methyl acrylate, methyl methacrylate, vinyl acetate, acrylonitrile,

or vinylpyridine.

For example, a copolymer from three parts of CH2 CHOC2H4NHCONHCE and one part of methyl acrylate, or methyl methacrylate, or vinyl acetate is soluble in Water even though homopolymers of the latter are not.

Polymerization may also be carried out by techniques useful for forming copolymers in dispersion in aqueous systems. Here a mixture of a ureidoalkyl vinyl ether and another polymerizable vinylidene compound without or with an inorganic solvent is dispersed or suspended in, water. An emulsifier and/or dispersing agent may be used. The mixture. is usually stirred. A polymerization cataylst is added, or catalyst and activator and, if desired, modifiers, such as butters, metal ions, mercaptans, and the like. Ordinarily dispersions containing 10% to 60% of polymerizable materials are used. Temperaturesv from below 0 C. to C. may be used. The preferred temperature range is 15' to 60 C.

1n bulk interpolymerizations one or more ureidoalkyl vinyl ethers are mixed with one or more other polymerizable vinylidene compounds and a polymerization catalyst is added. The mixture is maintained at a temperature at which the catalyst is effective for promoting polymerization until reaction is essentially complete. The copolymerization is best carried out under an inert atmosphere.

The polymers of this invention are useful in the fields of paper, coatings, and textiles. The water-dispersible types can be incorporated in spinning dopes such as ouprammonium cellulose to impart insolubility of the final films or fibers. The solvent-soluble types can be incorporated in cellulose acetate, nylon, or polyacrylonitrile dopes to improve the properties of fibers and films therefrom. The polymers themselves can be used to give coatings on paper, for example. They can be applied to textile fibers as finishing agents. The water-soluble and readily water-dispersible polymers, such as the homopolymer of CH2 CHOC2H4NHCONHCH3 are useful as whiteness builders or whiteness retention agents for built detergent systems, especially those containing alkyl aryl sulfonates,'such as sodium isopropylnaphthalene sulfonate, sodium octyl-phenyl sulfonate and so on.

When certain of the polymers as pointed out above are heated they become crosslinked and insoluble. The latter also react with cellulose, wool, silk, and the like. When large substituents are present, the treated substances become water-repellent. The latter polymers may likewise be mixed with other coating materials. When the films formed from the mixture are heated, crosslinking coupled with solvent resistance is obtained. The latter polymers also react with formaldehyde to form interesting and novel methylol derivatives. These are soluble, reactive condensates which are rendered insoluble when heated.

The water-soluble condensates are particularly useful for imparting wet strength to paper. They are useful for bonding rubber to fabric, including tire cord. They are useful for stabilizing wool. These hydroxymethyl com- 11 pounds can be reacted with alcohols to yield ether derivatives, the simple alcohols yielding the corresponding alkoxymethyl derivatives. These are particularly useful in coating compositions.

The following examples are illustrative of the invention:

Example I (a) A solution of 44 g. (0.5 mole) of Z-aminoethyl vinyl ether in 50 ml. of dry benzene was cooled to C. and treated dropwise with a solution of 35.5 g. (0.5 mole) of ethyl isocyanate in 50 ml. of dry benzene with con commitant stirring. The reaction was maintained at 0-5 C. during the addition and allowed to stir and warm to 30 C. during a period of 30 minutes. The benzene was removed by stripping under reduced pressure, and the product, amounting to 79 g., was isolated as the residual solid. Purification was effected by recrystallization of the product from a mixture of benzene and petroleum ether to give 73 g. of a white crystalline solid, M. P. 55 -57 C., soluble readily in water, methanol or acetone. It contained upon analysis 52.9% C, 8.6% H, and 17.7% N. The corresponding theoretical values for N-(2-vinyloxyethyl)N-ethylurea,

are 53.2% C, 8.87% H, and 17.7% N. Infrared analysis indicated the presence of a vinyl group which was confirmed by titration with iodine solution.

(b) This material is useful as a bacteriostatic agent showing a 9 mm. zone of inhibition when tested by the Standard Agar-plate technique against M. pyogenes var.

aureus.

(c) This material is also useful as a special solvent for coupling oil and water-soluble agents such as alkylphenoxypolyethoxyethanols. Clear solutions of water in the amounts of -10% in kerosene or oil solutions of l-10% of ethylene oxide condensates are obtained by the inclusion of l-10% of this vinyloxyethylurea.

(d) The product of this example is useful in the modification of aminoplasts particularly aqueous urea-formaldehyde condensates designed for use as adhesives such as for plywood. Amounts of the N-ethyl-N'-vinyloxyethyl urea from 5-25 are used to replace a corresponding amount of urea in an adhesive condensate. For example 0.25 part of the vinyloxyethyl urea, 0.75 part of urea and 1.7 parts of formaldehyde as a 37% aqueous solution are combined and condensed at pH 7.8-8.2 until the desired degree of Water-tolerance is achieved. This condensate shows a greatly improved storage stability as compared to a similar resin prepared entirely from urea. This modified urea condensate is used with an acid or acid-producing catalyst such as ammonium thiocyanate and applied to wood panels. The resultant cures are faster or can be obtained at lower temperatures than with conventional urea resins and the resultant bond shows an increased degree of hot water resistance. Similar advantages are obtained when this vinyloxyethylurea is added to carbamate or melamine-formaldehyde condensates and similar nitrogenous resin-formers.

(e) The compound of this example may be converted to a methylol derivative with aqueous or alcoholic solutions of formaldehyde by warming such mixtures at 40- 100 C. at a pH of 8.5-9.5 for 1-4 hours. The methylol derivative may also advantageously he added to amino plast condensates.

(f) In a like manner, the following condensations were effected by the procedure of part (a) hereinabove:

1. Methyl isocyanate and 3-aminopropyl vinyl ether 2. Ethyl isocyanate and '2-N-mcthylaminoethyl vinyl ether 3. n-Dodecyl isocyanate and Z-N-(Z-hydroxyethyl) aminoethyl vinyl ether 4. n-Octadecyl isocyanate and Z-N-henzylaminoethyl vinyl ether '12 5. Ethyl isocyanate and Z-N-p-chlorophenylaminoethyl vinyl ether 6. Cyclohexyl isocyanate and Z-N-octadecylaminoethyl vinyl ether 7. Isobutyl isocyanate and Z-N-cyanoethylarninopropyl vinyl ether 8. Allyl isocyanate and 2-aminoethyl vinyl ether 9. Ethyl isocyanate and 2-N-oleylaminoethyl vinyl ether 10. Ethyl isocyanate and Z-N-crotylaminoethyl vinyl ether.

(g) Homo-polymerizati0n.These monomers except for the N-methyland N-ethyl-N-vinyloxyethyl ureas were not water-soluble and were therefore best polymerized in bulk or in solution in dimethylformamide. Those with long alkyl substituents like dodecyl were toluene-soluble and could be polymerized in that solvent. In general, about 2% by weight of monomer of dimethyl azoisobutyrate was employed as the initiator to give 40%-l00% conversions. Amounts of initiator from 05-10% can be used.

(h) Fifty grams of N-vinyloxyethyl-N-ethyl urea was melted in a small flask equipped with a stirrer by heating the flask and contents to 60 C. The air in the flask was displaced with nitrogen and one gram of dimethyl azoisobutyrate added and uniformly mixed with the monomer by stirring. The temperature was adjusted to 65 C. and the reaction was maintained at this temperature in an inert atmosphere for 20 hours. The product was a light-yellow, viscous resin which set to a tacky glass upon cooling. The residual monomer and low-molecular weight polymer was separated by extraction with dry acetone. The polymer, amounting to 20 g., remained as a white powder, insoluble in acetone or water but soluble in methanol, butanol or a mixture of acetone and water.

(i) A solution of the polymer (of part (12)) in butanol containing 30% by weight of solids was applied to panels of glass, metal, and masonite. The panels were dried by heating at C. for 5 minutes after a 30 minute air-dry. The resultant films were hard and glossy with fair adhesion. The films could be dissolved again in butanol. Similar solutions were prepared and treated as follows:

1. Formaldehyde, 20% by weight of resin, and butyl acid phthalate, 4% by weight of resin, were added.

2. N,N-bismethoxymethylethylene urea, 20% by weight of resin, and p-toluenesulfonic acid, 1% by weight of resin were added.

Each mixture was again filmed onto panels of glass, metal and masonite, air-dried for 30 minutes and heated at 150 C. for 10 minutes. Again the films were hard and glossy. The adhesion was improved and the films were now resistant to water, soap-solutions, and organic solvents.

The presence of an alkyl group on each nitrogen of the N-ethyl-N-vinyloxyethyl urea had two unexpected and surprising eflects. The first was the insolubility of the homo polymer thereof in water even-though the monomer was thus soluble. The second was the stability of solutions of the polymer against further self-condensation of a non-vinyl character which is in marked contrast with the characteristic of vinyloxyalkyl urea polymer having two hydrogen atoms on one nitrogen to readily under-' go such further condensation. The less polar nature of the N,N-disubstituted urea and its polymer resulted in a greatly decreased sensitivity of resultant coatings and films to moisture and wider compatability of the polymers with organic solvents.

A solution of the polymer (of part (11)) in methanol is useful as a coating solution for application to plastic coatings such as those of poly(methyl methacrylate) to prevent surface-marring and reduce the build-up of static charges. The polymer may be applied from aqueous methanol or acetone toDacron, nylon, Orlon or other synthetic filament and staple yarns as a warp-size. Such 13 treatment greatly increases the weaving time between yarn breaks and reduces pilling and fuzz-balling.

(k) A solution of the polymer (of part (h)) in acetone containing 10% by volume of water may be added to acetone solutions of cellulose acetate in amounts of l25% or more by weight of polymer based on acetate and the mixture then coagulated into films or fibers. The treated acetate shows improved tensile properties and a change in wet-tensile and dyeability dependent on the amount of urea polymer present. Such fibers and films may be further changed by including formaldehyde or acetaldehyde and acid in the original spinning solution or by aftertreating the fibers or films therewith. Such fibers or films when cured as by heating at ZOO-300 F. for 10-60 minutes are solvent-insoluble and show less extensibility both dry and wet.

Similarly, other film-forming materials capable of being coagulated or regenerated from solution or formed by melt extrusion or spinning may be modified by inclusion of the polymeric urea again in amounts of l-25%. For example, a solution of an acrylonitrile polymer in dimethylformamide is mixed with five percent by weight of the polymeric urea and a fiber is formed by extrusion into a coagulating bath. The resultant fiber shows a greater alfinity for dyes than a corresponding unmodified polyacrylonitrile fiber. Similarly, copolymers of acrylonitrile or polymers and copolymers of vinyl chloride may be so modified with improvement in dyeability.

The polymer of this example is useful as in thickening solutions of various compounds in alcohol, acetone, or mixtures of water with these solvents. It is also useful as a dispersant particularly as a soil-suspending or redispersing agent.

(I) Polymethylol derivative of polymer of Example 1 (h).Although the polymer of Example 1 (h) is not soluble in water, it is readily soluble in a 37% solution of formaldehyde in water adjusted to a pH of 8.5. A solution of the polymer was prepared by adding one mole of the polymer to an aqueous solution containing two moles of formaldehyde per mole of the urea and heating the mixture at 10% to 60% solids at 60 C. for one hour. Titration of the resulting solution for free formaldehyde indicated that more than 50% of the urea groups had been converted to methylol groups. The resulting solution was also infinitely dilutable with water, the polymethylol derivative being water-soluble. This solution was stable for weeks at room temperature and for months if kept at 10 C. or less and at a pH greater than 7.0. If acidified to a pH lower than 5.0, the polymer becomes insoluble and the solution forms a gel slowly at room temperature and rapidly if warmed.

The polymethylol compound can be isolated as a buff solid by freeze-drying or carefully spray-drying the alkaline, aqueous solution. The powder is quite stable and can be redissolved in water to give clear solutions useful in coatings, laminates, textiles and molding compositions.

(m) A wool fabric was padded through a 10% solution of the polymethylol compound of part (1) containing triethylamine phosphate at 0.5% so that the fabric gained between 2 and 5% by weight of resin. The fabric was then dried and cured at 300 F. for ten minutes. The resultant fabric after 300 minutes of washing in a launderometer showed less than 5% area shrinkage compared to 40% for an untreated control. The fabric had a somewhat crisp though not undesirable hand.

(n) Twenty parts of the polymethylol resin of part (I) as a 40% aqueous solution was added to 100 parts of a resin prepared by the condensation of diethylene glycol dicarbarnate with formaldehyde and methanol at 40% in a methanol-water mixture. The resultant mixture was catalyzed with p-toluenesulfom'c acid and filmed on glass and masonite panels. In one hour, tack-free, glossy films had formed that showed fair resistance to water and methanol. A ten minute cure at 60 C. gave water-re- 14 sistant films. Similar films prepared without the addition of the polyurea resin showed no water-resistance.

(o) The dried, relatively anhydrous polymethylol compound of part (I) was mixed with a slurry of sawdust and urea-formaldehyde condensate containing ammonium thiocyanate. The product was molded and heated in a press at pounds at 150 C. for 10 minutes. The resulting briquet was hard, smooth and much more waterresistant than a corresponding control prepared without the aforesaid polymethyol compound. Similarly, paper was impregnated with the polymethylol solution, catalyzed with acid, laminated in a press and heated. The resultant product was hard and resistant to water, soap, and solvents.

(p) Alkylated polymethylol compounds may be prepared from the polymer of part (h) by reacting the polymer with formaldehyde in methanol, butanol or other alcohols in place of part or all of the Water used in part (k) hereof. The procedure is the same as described for the aqueous solution. Careful acidification of the methylol compound in an alcohol to pH 4.0 and warming at 60 -l00 C. for l-4 hours gives the corresponding polyalkoxymethyl-poly(N ethyl N vinoxyethyl urea). These compounds are readily solvent-soluble and useful as coating media along or modified by the addition of alkyd resins or other solvent-soluble coating materials, such as gums, rosin-ester, linseed-oil esters and the like. A typical composition comprises 40% of resin solids in a vehicle, such as xylene, the resin being composed of 25 parts of the polyalkoxymethyl derivative and 75 parts of a short-oil non-drying alkyd. This vehicle may be pigmented in the usual manner by ball or roller-milling and catalyzed with butyl acid phthalate. Coatings applied to bonderized steel and baked at C. for 30 minutes are hard, glossy, solvent and soap-resistant and useful as refrigerator or appliance finishes. They are characterized by good indoor and outdoor durability.

(q) The aqueous or alcoholic solutions of the polymethylol compound of parts (I) and (p) are also useful in the treatment of fabrics. Rayon material is padded through a solution of the polymethylol compound containing ethanolarnine hydrochloride. The rolls are adjusted so that a 2% resin pickup is obtained. The fabric is dried and cured at 280 F. for 12 minutes. The resulting material may now be laundered with less than 12% area shrinkage and has a full somewhat crisp hand. Nylon net may similarly be padded through the polymethylol solution to give a pickup of 5% resin solids. Subsequent cure and laundering give a durable, stiff finish desirable for this type of material.

(1') A mixture of 50 parts of N-ethyl-N'-vinyloxyethyl urea, 50 parts of N-octadecyl-N-vinyloxyethyl urea and 3 parts of dimethyl azoisibutyrate was stirred and heated at 65 for 8 hours in an atmosphere of nitrogen. The resultant polymer was a Waxy solid readily soluble in toluene. A solution of the polymer in toluene was emulsified by mixing with Water containing 0.5% of an octyl polyoxyethylene phenol containing an average of 30 ethylene oxide groups. The emulsion was exhausted onto cotton gabardine and the treated fabric dried. The resultant material was found to have a soft hand and to be waterrepellent. A second portion of fabric after treatment with the emulsion was dipped into a formaldehyde solution acidified to pH 3.5 and then dried and cured at 300 F. for 10 minutes. Again a soft, water-repellent fabric was obtained that retained its repellency after several drycleanings.

(s) A solution of 40 parts of ethyl acrylate, 50 parts of methyl methacrylate, 10 parts of N-ethyl-N-vinyloxyethyl urea, and 0.5 part of benzoyl peroxide in 250 parts of Z-ethoxyethyl acetate were added slowly to a stirred reaction vessel maintained at 80 C. by external heating. The rate of heating and addition was adjusted to maintain this temperature during the 2 hours required for the addition to be completed. An additional 0.5 part of benzoyl 15 peroxide in 50 parts of 2-ethoxyethyl acetate was added in two equal portions at 1 hour intervals while stlrrmg and maintaining the reaction at 80 C. The final product had a Gardner-Holdt viscosity of U+ at 38.8% SOlldS and was a light-yellow, clear resin solution.

Films prepared by casting this solution on glass or metal and baked at 125 C. for 30 minutes were glossy with a pencil hardness of H. A portion of the solution mixed with 20% by weight (on the resin) of bis-methoxymethylethylene urea and 1% of p-toluenesulfonic acid and again filmed and baked gave glossy films of improved adhesion and unaffected by immersion in cellosolve acetate for one hour. This mixture when pigmented with titanium dioxide, sprayed and baked, gave a glossy, white resistant finish eminently suited for refrigerators, washers, airconditioners, and other coated metal appliances.

In a similar manner, a coating containing a copolymer of 30 parts of acrylonitrile, 60 parts of methyl methacrylate and 10 parts of ethyl-vinyloxyethyl urea was prepared. When modified with the bis-methoxymethyl-ethylene urea and catalyst and baked, the films had a hardness of 7H and a microknife adhesion of 4.5 with excellent gloss, solvent and alkali-resistance.

(t) A charge of 10 parts by weight of N-ethyl-N'- vinyloxyethyl urea and 90 parts of butyl acrylate was placed in a closed vessel with 125 parts of water and 5 parts of t-octylpolyethyleneoxyethyl phenol having an average of 40 oxyethylene units per molecule. The mixture is agitated at 20 C. under a nitrogen atmosphere. Then 0.3 part of ammonium persulfate and 1 part of diethylene triamine were added and agitation continued. The temperature rose to 40-45" C. during copolymerization. The polymer dispersion obtained was stable to storage under normal conditions for several months. It was applied to panels of wood, glass and steel and the coatings were dried and baked at 125 C. When applied to a wool fabric in the proportion of 7% on the weight of the fabric, the fabric after 300 minutes of laundering showed greatly reduced shrinkage and a soft hand.

Example II (a) A solution of 14.1 g. (0.1 mole) of Z-isocyanatoisobutyl vinyl ether in 50 ml. of dry benzene was added slowly with stirring to 18.5 g. (0.1 mole) n-dodecylamine in 50 ml. of benzene in a flask maintained at 0-5 C. by means of an ice-bath. The rate of addition was adjusted to maintain the temperature below 10". When the addition was complete, stirring was continued for sixteen hours and the temperature was allowed to rise to 30. Volatiles and solvent were removed by stripping at reduced pressure to give 31 g. of product as a viscous, yellow oil that gradually solidified. The product was recrystallized from a mixture of methanol and water and found to melt at 3035, just about room temperature. It contained 8.3% nitrogen as compared to 8.59% demanded by theory for N-dodecyl-N-(1,1-dimethyl-2-vinyloxyethyl) -urea,

CH2 CHOCH2C(CHs) 2NHCONHC12H25 Thus, in place of dodecylamine, in part (a) hereof, substitute:

. Hydroxyethylamine Dimethylaminopropylamine Z-arninoethylpyridine i-chloropentylamine Methallylamine Dimethylamine Diethylamine \zm ll hullow -16 8. Di-(Z-ethylhexyl) amine 9. Dicyclohexylamine 10. Diethanolamine 11. Di(2-cyanoethyl)'arnine 12. Bis(3-dimethylaminopropyl) amine 13. Methylbenzylamine 14. Piperidine l5. Morpholine (0) By the procedure of part (a) hereof, 1,1,5-trimethyl-7-vinyloxyheptylisocyanate,

. Example 11! (a) A mixture of 50 parts of the dodecylvinoxyisobutyl urea of Example 11 (a) and one part of dimethyl azoisobutyrate were melted at40" C. and intimately mixed. Air was displaced in the container by nitrogen and the polymerization was eflected at 75 C. for sixteen hours to give a viscous resin. Monomer was separated by washing the resin with acetone. Seventeen parts of polymer, insoluble in acetone, methanol or heptane, was obtained. The polymer was a white solid, soluble in benzene.

(b) A solution of 100 parts of the urea of Example 11 (a), 100 parts of toluene, and 2 parts of dimethyl azoisobutyrate was heated in an inert atmosphere at 75 C. for sixteen hours. The polymer was isolated by precipitation with benzene and amounted when dried to 26 parts.

Example V (a) To a stirred, cooled solution of 83 parts of t-octyl- V CH2=CHOCHzCHzNHCONHCaHg-t This compound was found to be an excellent contact insecticide giving good control of red-spider miteswith no foliage injury. In addition, it gave good residual control and showed some activity as a mite ovacide. For example, a 12.5% emulsion concentrate prepared in Han solvent (a purified petroleum fraction) gave kill of red spiders when applied at 1 part in 800, no foliage injury and 22% control of'mite eggs. At 1 part in 3200 a 61% .kill was obtained.

In addition this compound is bacteriostatic showing a 9 mm. zone of inhibition against M. pyogenes var. aureus by the agar plate technique.

(b) By the procedure of part (0) hereof, the following compounds were reacted:

1. t-Butyl isocyanate and 2-aminodecyl vinyl ether 2. t-Dodecyl isocyanate (prepared from propylene tetramer) and 2-N-ethylaminoethyl vinyl ether 3. t-Tetracosanyl isocyanate (prepared from trimer) and 2-aminopropyl vinyl ether' 4. t-Octadecyl isocyanate (prepared from nonene dimer) and 2-aminobuty1 vinyl 'ether (c) A mixtureof 10 parts of the urea of part (a) octylene hereof and 0.15 part of dimethyl azoisohutyrate were melted at 60 C. and mixed. Polymerization was effected by heating the mixture in an inert atmosphere for 20 hours at 75 C. The resultant product was a white, hard resin that was purified by solution in toluene and precipitation with petroleum ether. Repetition of this process gave 4.3 parts of pure polymer as a white solid, soluble in toluene.

Example V A solution of 39.5 g. (0.25 mole) of 3-methyl-3-nitrobutylisocyanate in 60 ml. of dry benzene was cooled, stirred and treated dropwise with 21.8 g. (0.25 mole) of Z-aminoethyl vinyl ether while the temperature was maintained at 10 C. by means of an ice-bath. When the addition was complete, the reaction was warmed to 70 C. and then cooled. Solvent was removed in vacuo and the product obtained as a viscous mass that gradually crystallized. Several recrystallizations from a mixture of methanol and water gave a pure product, M. P. 50-55- C., containing 49.2% carbon, 7.71% hydrogen and 17.16% nitrogen. The theoretical values for N-vinyloxyethyl-N-(3-methyl-3-nitrobutyl) ureas CH2=CHOCHzCHzNHCONl-ICHzCHzCXCHs)zNOz are 49.0% carbon, 7.76% hydrogen, and 17.15% nitrogen.

The requisite isocyanate was prepared from the adduct of 2-nitropropane and ethyl acrylate by hydrolysis to the acid, conversion to the acid chloride, thence to the azide with sodium azide and thermal rearrangement to the isocyanate. The important intermediates are formulae ized below:

Example VI (a) A solution of 60.0 g. (1.0 mole) of ethyl isocyamate in 100 ml. of benzene was added to a stirred, cooled solution of 130 g. 1.0 mole) of S-aminopentyl vinyl ether in 150 ml.of benzene. The solution was maintained at -5. C. during the addition and for 30 minutes thereafter. The product precipitated from the reaction mixture and was" isolated by filtration as white, shiny plates. When dry, they amounted to 160 g., an 84% yield, M. P. 75 -77 C. and contained 13.7% nitrogen and at least 14.4% vinyl by iodine titration. The theoretical values for N-ethyl-N'-vinyloxypentyl urea CH2=CHO (CH2 5NHCONHC2H5 are 14.7% N and 15.2% vinyl.

(b) In a similar manner the following compounds were reacted:

3. Methyl isocyanate and Z-amino-l-hexadecylethyl vinyl ether Example VII (a) A mixture of 69 g. (0.5 mole) of potassium carbonate, 150 ml. of water, 100 ml. of toluene and 57.5 g. (0.5 mole) of 2-amino-2-methylpropyl vinyl ether was stirred, cooled and treated with 53.5 g. (0.5 mole) of dimethylcarbamyl chloride in 100 ml. of toluene. When the addition was complete the mixture was heated to reflux for 2 hours, cooled, filtered and the layers separated. The organic layer was dried, concentrated and distilled and a heart cut, B. F. 86 C./0.5 mm., selected for analysis. This fraction crystallized upon standing and contained 14.8% nitrogen and 17.9% vinyl ether by 1.8 iodine itra i n- The ztl edte ai va ue i 7 NiN-dimetlr y '-(1.1- m thy z vi ylcxvethyl) rea are 15.1% nitrogen and 23.1% vinyl ether. Infrared analy is indicated the pre ence of a nyl ether group a reaction with y ro iylemiu hyd ochlor d s e the theoretical value for acetaldehyde,

(b) A mixture of 115 g. (1.0 mole) of Z-amino-Z- methylpropyl vin ether and .m -Int lue was stirred and treated with 53.5 g. (0.5'mole) of dimethylcarbamyl chloride while maintaining the temperature at 40 -5 0 C. Anexotherm .Was observed that lasted about one hour after which the reaction was warmed at 50 C. for two hours. The mixture waslcooled and then added slowly to 30 g. of caustic dissolved in '200 ml. or water. The layers were separated andthe organic layer was dried and concentrated to glue :the product as an oil that solidified immediately on cooling. Recrystallization from aqueous ethanol gave 45 g. of white crystals, M. P. 59- 61" C., readily soluble in ethylene dichloride, benzene, ethyl acetate, dioxane, methanol or chloroform and insoluble in hot or cold water.

- The compound was found to be a bacteriostatio agent giving a 9 mm. zone of inhibition against M. pyo'genes var. aureus When'tested onan agar plate. i

(0) By the procedures of parts (a) and (5) hereof,

the following were reacted:

D hyl a amy ch o i e and -s methy -ami 0 octyl vinyl ether y ylea bamvl chl r de and .Z am nozl-mc hyl P1'9PY1 ny the (d) Bulk polymerization of the urea .of part (a) hereof by means or 2 percent by weight of dimethyl .azoisobutyrate at 75 gave a .clear, yellow resin, hard to the touch with excellent adhesion to glass.

Example VIII Y the PTQQQQQHE .Qf Example VII (4) there were reacted:

1. Dimethylcarbamyl chloride and A-an mjnobutyl vinyl ether Didodscylcarbamyl ch q ide and flamiuodecy i y ether The result n ;m'aa der vatives we e polym r bulk procedure of Example VII (d). The final polymers were clear, slightly YQHQW solids a; room temperature.

- Example 1X (a) There were reacted as in Example VII (a):

(b) The resulting monomers were polymerized by the procedure of Example VII (d). The solid polymers obtained were clear, slightly yellowish products, which were readily soluble in one or more of such solvents as acetone, dioxane, dimethylformamide, dimethylacetamide, acetonitrile and nitromethane to produce solutions from which coatings, films, and variously shaped products were obtained.

A copending application of the present applicant with 19 Vincent J. Mozer, in the hands of a common assignee, having Serial No. 409,255,-fi1e'd' February 9,1954, claims papers having 'wef strength obtained by the incorporation ofcompounds. disclosedpnd; claimed herein in the paper andprocesses f o r making such paper.

fI claimz-"Q j 7 r n '1. xeaapps'inohbr matter comprising ,a. compound se'lectdfroiri the group consisting of; I p

r CI-Ia:CHO A NRCNHR' it CH2;CH0-A-NR CONR"R GI-Ia:CI:IO Y Q(Rf) R Nl-I'Ci'lllR'R .r t 0 t .GHflCHOrZrNHCONR'R. V wherein A is selectcdirom the group consisting of the cyclohexyle'ne group and alkylene' groups of 2 to 18 carbon atoms; of' which-a chain ofat least two is connected between the adjoining nitrogenian'd oxygenatoms, R is selected-from the-group- COHSiSfiIIgfOf hydrogen and a monovalent hydrocarbon group of 1.to '18 carbon atoms, R'- 1' s-selected-from1the group consisting of aliphatic and cycloaliphaticihydrocarbon groups 'of 11 to" 24 carbon atoms, R is a monovalent.hydrocarbonvgroup of 1 to 18; carbon atoms, R -is;selected-fr"om"the group consisting of -aliphatic andcycloaliphatichydrocarbon' groups of l to 24 carbon atoms,--Y-is an-alkylene group of 1 to 2 carbon atoms,-R is an alk'yl groupof -l to 4 carbon atoms, R is an alkyl group of .l to-4 carborr atoms, and Z is selected I from the group consisting of the cyclohexylene group ahd'alkylene groupspfd to 18 carbon atoms of which a chainoi at least 4 is co'nnected between the adjoining nitrogen and oxygen atomafl 2. A composition of matter comprising a polymer of acompound-definedinclaim v t 3;'A composition of'niatterj'c omprisinga copolymer of a compound; defined'imciaim l with another monoethylenically unsaturated monomer.- a

4. A composition of-matter comprising a compound having the formula v 4 H V CHzrCHO-A-NRCONHR' wherein A-is an alkylene group vof 210.18 carbon atoms, of which a chain of at leasttw'o is connected between the adjoining nitrogen and oxygen atoms,-R ishydrogen, and R is an aliphatic hydrocarbon group of 1 to 24 carbon atoms. 5; Acomposition of matter comprising a polymer of a compound of claim 4. 2 6.;AI composition'of' matter comprising a compound havingthe'formula i I CHz:CHO-'ANR?CONR'R wherein A is an alkylene groupof 2 to 18 carbon atoms,

of which a chain of at least two is connected between the adjoining nitrogen and oxygen atoms, R is a monovalent aliphatic hydrocarbon group of 1 to 18 carbon atoms, R'

is an aliphatic hydrocarbon group of 1 to 24 carbon atoms, and R is an aliphatic hydrocarbon group of l to 24 carbon atoms.

7. A composition of matter comprising a polymer of a compound of claim 6.

8. A composition of matter comprising a compound having the structure of formula wherein Z is an alkylene group of 4 to 18 carbon atoms of which a chain of at least 4 is connected between the adjoining nitrogen and oxygen atoms, R is an aliphatic hydrocarbon group of 1 to 24 carbon atoms, and R is an aliphatic hydrocarbon group of 1 to 24 carbon atoms,

11. A composition of matter comprising a polymer of a compound of claim 10.

12. A composition of matter comprising N-ethyl-N- yinyloxyethyl urea.

' 13. A composition of matter comprising a polymer of N-ethyl-N'-viny1oxyethyl urea.

14. A composition of matter comprising N-n-dodecyl- N-vinyloxyisobutyl urea.

15. A composition of matter comprising a polymer of N-n-dodecyl-N'-vinyloxyisobutyl urea.

16. A composition of matter comprising N-t-octy1-N'- vinyloxyethyl urea.

17. A composition of matter comprising CH2:CHOC2H4N(CI-I3)CON(CHa)2 18. A composition of matter comprising CH2:CHOCH2C(CH3)2NHCON(CH3)2 References Cited in the file of this patent UNITED STATES PATENTS 

1. A COMPOSITION OF MATTER COMPRISING A COMPOUND SELECTED FROM THE GROUP CONSISTING OF: 